Comprehensive Evaluation of the Volatomic Fingerprint of Saffron from Campania towards Its Authenticity and Quality

The volatile profiles of eight saffron samples (seven cultivated and one spontaneous) grown in different geographical districts within the Campania region (southern Italy) were compared. Using headspace solid-phase microextraction coupled to gas chromatography–mass spectrometry (HS-SPME/GC-MS), overall, 80 volatiles were identified in the eight landraces. Among them, safranal and its isomers and other related compounds such as isophorones, which are not only key odorants but also pharmacologically active metabolites, have been detected in all the investigated samples. Principal Component Analysis performed on the volatiles’ compounds revealed that the spontaneous sample turned out to be an outlier. In particular, the volatile organic compounds (VOCs) profile of the spontaneous saffron presented four lilac aldehydes and four lilac alcohol isomers, which, to the authors’ knowledge, have never been identified in the volatile signature of this spice. The multivariate statistical analysis allowed the discrimination of the seven cultivate saffron ecotypes in four well-separated clusters according to variety. Moreover, 20 VOCs, able to differentiate the clusters in terms of single volatile metabolite, were discovered. Altogether, these results could contribute to identifying possible volatile signature metabolites (biomarkers) or patterns that discriminate saffron samples grown in Campania region on a molecular basis, encouraging future biodiversity programs to preserve saffron landraces revealing valuable genetic resources.